CN105794023A - Positive electrode for non-aqueous electrolyte secondary battery - Google Patents

Positive electrode for non-aqueous electrolyte secondary battery Download PDF

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Publication number
CN105794023A
CN105794023A CN201480064797.XA CN201480064797A CN105794023A CN 105794023 A CN105794023 A CN 105794023A CN 201480064797 A CN201480064797 A CN 201480064797A CN 105794023 A CN105794023 A CN 105794023A
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China
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battery
lithium
transition metal
containing transition
metal oxide
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国分贵雄
小笠原毅
新名史治
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

Provided is a positive electrode for a non-aqueous electrolyte secondary battery able to minimize any decrease in initial efficiency even when a positive electrode exposed to air is used. According to one aspect of the positive electrode for a non-aqueous electrolyte secondary battery of the present invention, the positive electrode for a non-aqueous electrolyte secondary battery contains positive electrode active material particles in which rare earth compounds are attached to the surface of transition metal oxides containing lithium, and a boron compound.

Description

Positive electrode for nonaqueous electrolyte secondary battery
Technical field
The present invention relates to positive electrode for nonaqueous electrolyte secondary battery.
Background technology
In recent years, the personal digital assistant device such as mobile phone, notebook computer, smart mobile phone small-sized/lightweight develops rapidly, requires further high capacity as its secondary cell driving power supply.Along with discharge and recharge, lithium ion moves between positive and negative electrode thus the rechargeable nonaqueous electrolytic battery carrying out discharge and recharge has high-energy-density, and is high power capacity, and therefore the driving power supply as personal digital assistant device as described above is widely used.
And then, recently, rechargeable nonaqueous electrolytic battery is also affected by paying close attention to as the power power supply of electric tool, electric automobile (EV), mixed power electric car (HEV, PHEV) etc., it is anticipated that the further expansion of purposes.For such power power supply, it is desirable to the output characteristics when high capacity that can use for a long time, within a short period of time repeat high current charge-discharge improves.Particularly, in the purposes such as electric tool, EV, HEV, PHEV, it is necessary to maintain the output characteristics under high current charge-discharge and reach high capacity.
Such as, following patent documentation 1 implys that, by there is the 3rd race's element of periodic chart on the surface of positive active material mother metal granule, thus the deterioration of the preservation characteristics that charges that the decomposition reaction of electrolyte that the interface at positive active material with electrolyte produces causes can be suppressed when improving charging voltage.
It addition, following patent documentation 2 illustrates, boronic acid compounds is made to adhere to the positive active material of at least one and the lithium comprised in nickel and cobalt and carry out heat treated, such that it is able to realize the raising of high capacity and efficiency for charge-discharge.
Prior art literature
Patent documentation
Patent documentation 1: International Publication WO2005/008812 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-146739 publication
Summary of the invention
The problem that invention to solve
Even if it will be appreciated, however, that adopt the technology disclosed in above-mentioned patent documentation 1 and 2, when positive active material, positive pole are exposed to air, the reduction of initial efficiency also cannot be suppressed.
A scheme according to the present invention, its object is to, it is provided that even if also can suppress positive electrode for nonaqueous electrolyte secondary battery and the positive electrode active material for nonaqueous electrolyte secondary battery of the reduction of initial efficiency when using the positive active material after being exposed to air, positive pole.
For solving the scheme of problem
A scheme according to the present invention, positive electrode for nonaqueous electrolyte secondary battery comprises: the surface attachment at lithium-containing transition metal oxide has positive active material granule and the boron compound of rare earth compound.
It addition, a scheme according to the present invention, positive electrode active material for nonaqueous electrolyte secondary battery comprises: lithium-containing transition metal oxide；It is attached to the rare earth compound on the surface of above-mentioned lithium-containing transition metal oxide；Boron compound with the surface being attached to above-mentioned lithium-containing transition metal oxide.
The effect of invention
A scheme according to the present invention, it is provided that: even if also be able to suppress positive electrode for nonaqueous electrolyte secondary battery and the positive electrode active material for nonaqueous electrolyte secondary battery of the reduction of initial efficiency when using the positive active material after being exposed to air, positive pole.
Accompanying drawing explanation
Fig. 1 is the schematic elevational view of the rechargeable nonaqueous electrolytic battery illustrating one aspect of the present invention.
Fig. 2 is the schematic sectional view of the line A-A along Fig. 1.
Detailed description of the invention
Hereinafter embodiments of the present invention are illustrated.Present embodiment is implement an example of the present invention, and the present invention is not limited to present embodiment.
< rechargeable nonaqueous electrolytic battery >
One example of embodiments of the present invention and rechargeable nonaqueous electrolytic battery possess positive pole, negative pole and nonaqueous electrolyte.An example as rechargeable nonaqueous electrolytic battery, for instance following structure can be enumerated: positive pole and negative pole are incorporated in the outer tinning of battery across nonaqueous electrolyte and the nonaqueous electrolytic solution of separator winding or the electrode body being laminated and liquid, but are not limited to this.
Herein, as illustrated in figures 1 and 2, the concrete structure of above-mentioned rechargeable nonaqueous electrolytic battery 11 is as follows: positive pole 1 and negative pole 2 across the corresponding configuration of separator 3 and wind, and are impregnated with nonaqueous electrolytic solution in the electrode body of the platypelloid type formed by these positive and negative polarities 1,2 and separator 3.Above-mentioned positive pole 1 and negative pole 2 are connected to positive pole collector plate 4 and negative pole collector plate 5, formed as secondary cell can the structure of discharge and recharge.It should be noted that above-mentioned electrode body is configured in the accommodation space of the aluminium lamination pressure shell body 6 possessing the heat-sealing portion 7 being heat-sealed between periphery.Hereinafter, an example of present embodiment and each member of formation of rechargeable nonaqueous electrolytic battery are illustrated.
[positive pole]
One example of embodiments of the present invention and positive electrode for nonaqueous electrolyte secondary battery comprise: the surface attachment at lithium-containing transition metal oxide has positive active material granule and the boron compound of rare earth compound.Just highly preferred it is made up of positive electrode collector and the positive electrode material mixture layer being formed on positive electrode collector.Positive electrode collector such as can use: has the metal formings stable in the potential range of positive pole such as the thin-film body of electric conductivity, particularly aluminum, Alloy Foil, have the thin film of the metal surfaces such as aluminum.In positive electrode material mixture layer, except positive active material granule, it is preferable that comprise binding agent, conductive agent.
Existence due to the rare earth compound of the surface attachment at lithium-containing transition metal oxide, by being exposed to the reason of the deterioration in characteristics that air causes and LiOH reaction of formation (particularly as follows: be present in the moisture on the surface of lithium-containing transition metal oxide and lithium-containing transition metal oxide reacts, cause the Li of the surface layer being positioned at lithium-containing transition metal oxide and the displacement reaction of hydrogen, thus, capture Li from lithium-containing transition metal oxide and generate the reaction of LiOH) it is suppressed, reduce such such that it is able to carry out efficiency for charge-discharge during discharge and recharge after reducing the exposure to air, by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes.
Additionally, due to the existence of boron compound contained in positive pole, cause that the surface of lithium-containing transition metal oxide can reduce, it is possible in suppression air, the moisture of existence is to the absorption of lithium-containing transition metal oxide.Thinking, this act as the interaction obtained when boron compound coexists with rare earth compound, and boron compound and rare earth compound cannot obtain when not coexisting.Additionally, owing to moisture is suppressed to the absorption of above-mentioned lithium-containing transition metal oxide, the water quantities used in above-mentioned LiOH reaction of formation is caused also to tail off, therefore, can suppress further to be exposed to the reason of the deterioration in characteristics that air causes and above-mentioned LiOH reaction of formation, thus, it is possible to reduce the exposure to the deterioration of the initial stage charge-discharge characteristic that air causes further.By playing such synergy, it is possible to suppressing by being exposed to the reason of the deterioration in characteristics that air causes and above-mentioned LiOH reaction of formation, it is as a result, it is possible to significantly reduce by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes.
Additionally, lithium-transition metal composite oxide contains nickel and manganese, the molar ratio of nickel is more than the molar ratio of manganese, and the difference of the molar ratio of nickel and manganese is more than 0.25.As such lithium-transition metal composite oxide, it is possible to use nickel manganese compound, nickel cobalt manganese compound.Particularly, as nickle cobalt lithium manganate, it is preferred to use the material that molar ratio is 5:3:2,6:2:2,7:1:2,7:2:1,8:1:1 of nickel and cobalt and manganese.Particularly, from the view point of be possible not only to increase positive electrode capacity further and be more prone to above-mentioned LiOH reaction of formation, using the ratio material more than the ratio of manganese of nickel, nickel and the difference of the molar ratio of manganese when the mole that transition metal is overall is set to 1 are more than 0.25.It addition, they can be used alone can also mix use.
It should be noted that when the difference of the molar ratio of nickel and manganese is more than 0.60, LiOH reaction of formation is very easy to produce, therefore, nickel is preferably less than 0.60 with the difference of the molar ratio of manganese.
And then, in an example of present embodiment and positive electrode for nonaqueous electrolyte secondary battery, positive active material granule is also attached with boron compound preferably in the surface of lithium-containing transition metal oxide.Thus, it is possible to play synergy produced by above-mentioned rare earth compound and boron compound further, further improve by the reduction being exposed to the initial stage charge-discharge characteristic that air causes.
As rare earth compound, it is preferred at least one compound in the hydroxide of rare earth, oxyhydroxide, oxide, carbonate compound, phosphate cpd and fluorine compounds.Wherein, it is particularly preferred to at least one compound in the hydroxide and oxyhydroxide of rare earth, when using these rare earth compounds, it is possible to play further and suppress by being exposed to the effect that the initial efficiency that air causes reduces.This is because, the hydroxide of rare earth and oxyhydroxide increase the reaction activity of LiOH reaction of formation further.
As rare earth element contained in rare earth compound, it is possible to enumerate: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutecium.Wherein, it is particularly preferred to neodymium, samarium, erbium.This is because, the compound of neodymium, samarium, erbium is compared with other rare earth compounds, mean diameter is little, spreads more evenly across on the whole surface of lithium-containing transition metal oxide granule and easily precipitates out.
Concrete example as rare earth compound, it is possible to enumerate: oxide, the fluorine compounds etc. such as phosphate cpd, carbonate compound, Dineodymium trioxide, Disamarium trioxide, Erbia, neodymium fluoride, samaric fluoride, ErF_3 films such as the hydroxide such as Neodymium hydroxide, hydroxyl oxidize neodymium, Samarium trihydroxide., hydroxyl oxidize samarium, erbium hydroxide, hydroxyl oxidize erbium, oxyhydroxide and neodymium phosphate, samaric orthophosphate, phosphoric acid erbium, neodymium carbonate, samaric carbonate, carbonic acid erbium.Wherein, from can uniformly disperse the whole of granule and adhere to and be easily optionally present in the viewpoints such as particle surface further, it is particularly preferred to above-mentioned hydroxide, oxyhydroxide.
Mean diameter as rare earth compound, it is preferred to more than 1nm and below 100nm, more preferably more than 10nm and below 50nm.When the mean diameter of rare earth compound is more than 100nm, the particle diameter of rare earth compound becomes excessive, and therefore, the granule number of the rare earth compound that the particle surface at lithium-containing transition metal oxide adheres to reduces.Its result, low temperature output improves effect and sometimes diminishes.On the other hand, when the mean diameter of rare earth compound becomes smaller than 1nm, the particle surface of lithium-containing transition metal oxide is covered densely by rare earth compound, therefore, the occlusion of the lithium ion in the particle surface of lithium-containing transition metal oxide or release performance reduce, and charge-discharge characteristic reduces sometimes.
Rare earth compound is preferably more than 0.005 mass % and below 0.5 mass % relative to the ratio (adhesion amount) of the gross mass of lithium-containing transition metal oxide in rare earth element conversion, more preferably more than 0.05 mass % and below 0.3 mass %.When above-mentioned ratio becomes smaller than 0.005 mass %, it is impossible to fully obtain the effect above produced by rare earth compound and boron compound, sometimes cannot suppress to be exposed the reduction of the initial stage charge-discharge characteristic caused by pole plate.On the other hand, during more than 0.5 mass %, cover the particle surface of lithium-containing transition metal oxide superfluously, sometimes expose initial stage charge-discharge characteristic with or without pole plate and all reduce.
It addition, above-mentioned lithium-containing transition metal oxide can also comprise other addition element further.Example as addition element, it is possible to enumerate: boron (B), magnesium (Mg), aluminum (Al), titanium (Ti), chromium (Cr), ferrum (Fe), copper (Cu), zinc (Zn), niobium (Nb), molybdenum (Mo), tantalum (Ta), zirconium (Zr), stannum (Sn), tungsten (W), sodium (Na), potassium (K), barium (Ba), strontium (Sr), calcium (Ca) etc..
As above-mentioned lithium-containing transition metal oxide, it is possible to enumerate the granule of mean diameter 2～30 μm, this granule can also be the form of the second particle that the primary particle of 100nm to 10 μm is combined into.
Herein, when manufacturing an example and the positive electrode for nonaqueous electrolyte secondary battery of present embodiment, it is possible to use the method adding the aqueous solution being dissolved with the compound comprising rare earth element in the suspension comprise lithium-containing transition metal oxide.
When utilizing said method, add in above-mentioned suspension and be dissolved with in the process of aqueous solution of the compound comprising rare earth element, it is desirable to by the pH regulator of suspension to more than 6 and less than 10 scope and keep constant.If this is because, pH becomes smaller than 6, then lithium-containing transition metal oxide can dissolve sometimes.On the other hand, if pH is more than 10, when then adding, in above-mentioned suspension, the aqueous solution being dissolved with the compound comprising rare earth element, the granule of rare earth compound formed partially and be attached to the state of a part on surface of lithium-containing transition metal oxide granule, the microgranule of rare earth compound forms the state on the whole surface that will not be uniformly dispersed and be attached to lithium-containing transition metal oxide granule.Its result, this is with following worry: the effect not only dropping low-surface-energy is uneven, and cannot give full play to the inhibition of above-mentioned LiOH reaction of formation on the whole surface of lithium-containing transition metal oxide granule.
As additive method, it is possible to enumerate: stirring lithium-containing transition metal composite oxides, while the spraying of lithium-containing transition metal composite oxides is dissolved with the aqueous solution of the compound comprising rare earth element, solution or the method carrying out dripping and adding；Lithium-containing transition metal composite oxides add the compound comprising rare earth element the method mechanically carrying out mixing.As the method mechanically carrying out mixing, Ishikawa formula such as can be used to grind the mixer (HIVISMIX etc. that PRIMIXCorporation manufactures) etc. of blender, dual shaft planetary mode, HosokawaMicronCorporation Nobilta, Mechanofusion etc. manufactured can be used in addition.
But, the microgranule making rare earth compound spreads more evenly across when the whole surface of lithium-containing transition metal composite oxide particle, in order to more effectively suppress the carrying out of the water adsorption above-mentioned LiOH reaction of formation when the surface of lithium-containing transition metal composite oxides, it is particularly preferred to the method adding the aqueous solution being dissolved with the compound comprising rare earth element in the suspension comprising lithium-containing transition metal composite oxides.
When the suspension comprising lithium-containing transition metal oxide adds the aqueous solution being dissolved with the compound comprising rare earth element, when merely carrying out in water, precipitate out with the form of hydroxide, when fluorine source is joined in suspension fully, it is possible to precipitate out with the form of fluoride.When being fully dissolved with carbon dioxide, precipitate out with the form of carbonate compound, when phosphate anion is joined in suspension fully, precipitate out with the form of phosphate cpd, it is possible to make rare earth compound precipitate out at the particle surface of lithium-containing transition metal oxide.It addition, by the dissolving ion controlling suspension, for instance the rare earth compound of the state of hydroxide and fluoride mixing can also be obtained.
Afterwards, it is possible to the granule of the lithium-containing transition metal oxide that rare earth compound precipitates out on surface is carried out heat treatment further.As heat treatment temperature, it is preferred to 80 DEG C to about 500 DEG C, more preferably 80 DEG C to about 400 DEG C.During lower than 80 DEG C, there is the fully dry worry expending the unnecessary time, during more than 500 DEG C, have following worry: a part for the rare earth compound being attached to surface reduces in the effect of the granule diffusion inside of lithium-containing transition metal composite oxides, suppression surface energy.Particularly, when being below 400 DEG C, rare earth element, in the internal basic indiffusion of granule of lithium-containing transition metal composite oxides, is optionally present in particle surface, and therefore, the effect dropping low-surface-energy becomes big.It addition, when making the hydroxide of rare earth be attached to surface, become oxyhydroxide at about 200 DEG C to about 300 DEG C, and then become oxide at about 450 DEG C to about 500 DEG C.Therefore, when 400 DEG C of heat treated below, the hydroxide of rare earth big for the inhibition of LiOH reaction of formation, oxyhydroxide optionally can be configured at particle surface, and can obtain being homogeneously dispersed in the state of whole particle surface, therefore can obtain the resistance to of excellence and be exposed to atmospheric.
As the compound comprising rare earth element dissolved in aqueous, it is possible to use: rare earth acetate, rare earth nitrate, rare earth sulfate, rare earth oxide or rare earth chloride etc. are dissolved in the material of water, organic solvent.It addition, the rare earth sulfate dissolving rare earth oxide in sulphuric acid, hydrochloric acid, nitric acid and obtaining, rare earth chloride, rare earth nitrate also become and the above-mentioned material that to be dissolved in water same, therefore can use.
As boron compound, it is preferred to boric acid, Lithium biborate, lithium metaborate, lithium tetraborate, wherein, it is particularly preferred to for lithium metaborate.When using these boron compounds, it is possible to play the effect suppressed by being exposed to the initial charge/discharge efficiency reduction that air causes further.
Boron compound is preferably more than 0.005 mass % and below 5 mass % relative to the ratio of the gross mass of lithium-containing transition metal oxide in boron element conversion, more preferably more than 0.01 mass % and below 0.2 mass %.When above-mentioned ratio becomes smaller than 0.005 mass %, sometimes cannot fully obtain produced by rare earth compound and boron compound effect, pole plate cannot be suppressed because being exposed to the deterioration in characteristics that air causes.On the other hand, when above-mentioned ratio is more than 5 mass %, correspondingly reducing with the amount of positive active material, therefore positive electrode capacity reduces.
As the method making the positive pole comprising boron compound, it is possible to enumerate: mechanically carry out in advance mixing and make its method adhered to by lithium-containing transition metal oxide and boron compound；And, in the operation that conductive agent, binding agent is mixing, the method adding boron compound together with conductive agent, binding agent.As the method mechanically carrying out mixing, Ishikawa formula such as can be used to grind the mixer (HIVISMIX etc. that PRIMIXCorporation manufactures) etc. of blender, dual shaft planetary mode, it is also possible to use HosokawaMicronCorporation Nobilta, Mechanofusion etc. manufactured.
The particle diameter of boron compound granule is preferably smaller than the particle diameter of lithium-containing transition metal oxide, it is particularly preferred to less than the 1/10 of the particle diameter of lithium-containing transition metal oxide.When boron compound is more than lithium-containing transition metal composite oxides, diminish with the contact area of lithium-containing transition metal oxide, have the worry that cannot give full play to effect.
Herein, boron compound is present in the vicinity of rare earth compound, in above-mentioned situation, it is also possible to obtain effect produced by above-mentioned boron compound and rare earth compound.That is, boron compound can be attached to the particle surface of lithium-containing transition metal oxide, it is also possible to is not attached to surface and is present near rare earth compound in positive pole.It should be noted that mixed by boron compound etc. when optionally making it be attached to the particle surface of lithium-containing transition metal oxide further in advance with lithium-containing transition metal oxide, the synergy of boron compound and rare earth compound becomes big, therefore particularly preferably.
It should be noted that, as positive active material, being not limited to be used alone the surface attachment at lithium-containing transition metal oxide has the positive active material granule of rare earth compound or has the situation of positive active material granule of rare earth compound and boron compound in the surface attachment of lithium-containing transition metal oxide.Above-mentioned positive active material granule and the mixing of other positive active materials can also be used.As this positive active material, as long as can make lithium ion reversibly embed/compound of deintercalation is just not particularly limited, for instance can use: there is the material etc. embedding the layer structure of deintercalation, spinel structure, olivine structural that can carry out lithium ion when maintaining stable crystal structure and being constant.It should be noted that when only using situation or the use not positive active material of the same race of positive active material of the same race, as positive active material, it is possible to use the material of same particle diameter, the material of different-grain diameter additionally can also be used.
As binding agent, it is possible to enumerate: fluorine system macromolecule, rubber series macromolecule etc..Such as fluorine system macromolecule, can enumerate: politef (PTFE), polyvinylidene fluoride (PVdF) or their modified body etc., as rubber series macromolecule, it is possible to enumerate: ethylene-propylene-isoprene copolymer, ethylene-propylene-diene copolymer etc..They can be used alone, it is also possible to combines two or more and uses.Binding agent can also use with the thickening agent combination such as carboxymethyl cellulose (CMC), poly(ethylene oxide) (PEO).
For conductive agent, for instance as material with carbon element, it is possible to enumerate: material with carbon elements such as white carbon black, acetylene black, Ketjen black, graphite.They can be used alone, it is also possible to combines two or more and uses.
One example of embodiments of the present invention and positive electrode active material for nonaqueous electrolyte secondary battery comprise: lithium-containing transition metal oxide, be attached to the rare earth compound on the surface of above-mentioned lithium-containing transition metal oxide and be attached to the boron compound on surface of above-mentioned lithium-containing transition metal oxide.Thus, it is possible to play above-mentioned synergy produced by above-mentioned rare earth compound and boron compound, it is possible to reduce by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes.
[negative pole]
As negative pole, it is possible to use the negative pole used all the time, for instance can obtain as follows: negative electrode active material and binding agent are mixed in water or suitable solvent, coating negative electrode collector and dry, carrying out rolling thus obtaining.Preferably, negative electrode collector uses has the thin-film body of electric conductivity, particularly stable in the potential range of the negative poles such as copper metal forming, Alloy Foil, has the thin film etc. of the metal surfaces such as copper.As binding agent, it is possible to use PTFE etc. in the same manner as the situation of positive pole, it is preferred to use SB (SBR) or its modified body etc..Binding agent can also use with the thickening agent combination such as CMC.
As above-mentioned negative electrode active material, if for can reversibly occlusion, release lithium ion material be just not particularly limited, for instance material with carbon element can be used；Si, Sn etc. carry out alloyed metal (AM) or alloy material, metal-oxide etc. with lithium.It addition, they can be used alone can also mix two or more use, it is also possible to the negative electrode active material combination that will carry out selected from material with carbon element and lithium in alloyed metal (AM) or alloy material, metal-oxide.
[nonaqueous electrolyte]
Solvent as nonaqueous electrolyte, it is possible to use the cyclic carbonates such as that all the time use, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate；The linear carbonate such as dimethyl carbonate, Ethyl methyl carbonate, diethyl carbonate.From the view point of high-k, low viscosity, low melting point, as the non-water solvent that lithium ion conductivity is high, it is particularly preferred to use the mixed solvent of cyclic carbonate and linear carbonate.Additionally, it is preferred that the volume ratio by the cyclic carbonate in this mixed solvent Yu linear carbonate is limited in the scope of 2:8～5:5.
Alternatively, it is also possible to use following material together with above-mentioned solvent: the compound that methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton etc. comprise ester；Propane sultones etc. comprise sulfonic compound；1,2-dimethoxy-ethane, 1,2-diethoxyethane, oxolane, 1,3-dioxane, 1,4-dioxane, 2-methyltetrahydrofuran etc. comprise the compound of ether；Butyronitrile, valeronitrile, heptane nitrile, succinonitrile, glutaronitrile, adiponitrile, pimelic dinitrile, 1,2,3-the third trimethylsilyl nitrile, 1,3,5-penta trimethylsilyl nitrile etc. comprise the compound of nitrile；Dimethylformamides etc. comprise the compound etc. of amide, further, it is possible to use the solvent that a part of their hydrogen atom H is replaced by fluorine atom F and obtained.
On the other hand, as the solute of nonaqueous electrolyte, it is possible to use the solute used all the time, for instance can use: fluorine-containing lithium salts and LiPF6、LiBF4、LiCF3SO3、LiN(FSO2)2、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiN(CF3SO2)(C4F9SO2)、LiC(C2F5SO2)3And LiAsF6Deng.And then, it is possible to use in fluorine-containing lithium salts, add (lithium salts (the such as LiClO comprising more than one elements in P, B, O, S, N, Cl of the lithium salts except fluorine-containing lithium salts4Deng)) material.From the aspect also forming stable overlay film in high temperature environments on the surface of negative pole, it is particularly preferred to comprise fluorine-containing lithium salts and using oxalate dentate as the lithium salts of anion.
Example as the above-mentioned lithium salts using oxalate dentate as anion, it is possible to enumerate: LiBOB (dioxalic acid Lithium biborate), Li [B (C2O4)F2]、Li[P(C2O4)F4]、Li[P(C2O4)2F2].Wherein, it is particularly preferred to be used in negative pole and form the LiBOB of stable overlay film.
It should be noted that above-mentioned solute can be used alone can also mix two or more use.
[separator]
As separator, it is possible to use the separator used all the time.Such as can use: polypropylene system, the separator of polyethylene, polypropylene-polyethylene Multi-layer separated part, be coated with the separator of the resins such as aromatic polyamides system resin on the surface of separator.
Furthermore it is possible to form the layer of the filler comprising inorganic matter used at the interface of the interface of positive pole and separator or negative pole and separator all the time.As filler, it is possible to use that use, adopt one or more the oxide in titanium, aluminum, silicon, magnesium etc., phosphate cpd and its surface hydroxide etc. to carry out processing and the material that obtains all the time.The forming method of above-mentioned packing layer can make with the following method: is directly coated with, at positive pole, negative pole or separator, the method that the slurry containing filler is formed；The sheet formed by filler is adhered to the method etc. of positive pole, negative pole or separator.
Embodiment
Hereinafter, to being used for implementing the solution of the present invention, enumerate experimental example and further describe.But, experimental example shown below is in order to an example of the positive electrode for nonaqueous electrolyte secondary battery for making the technological thought of the present invention embody, rechargeable nonaqueous electrolytic battery and positive electrode active material for nonaqueous electrolyte secondary battery is illustrated and example, and the present invention is not by any restriction of following experimental example.The present invention can suitably change in the scope not changing its purport and implement.
(the 1st experimental example)
(experimental example 1)
First, the composition of the rechargeable nonaqueous electrolytic battery of experimental example 1 is illustrated.
[making of positive active material]
[the Ni that will be obtained by coprecipitation0.55Mn0.20Co0.25](OH)2And Li2CO3In the way of the mol ratio that Li is overall with transition metal becomes 1.05:1, grind mortar by Ishikawa formula mix.Afterwards, by this mixture in air atmosphere, in 950 DEG C of roastings 10 hours, pulverize, thus obtaining the Li that average aggregate particle size is about 14 μm1.06[Ni0.55Mn0.20Co0.25]O2Shown lithium nickel manganese cobalt composite oxide.
Preparing the lithium nickel manganese cobalt composite oxide granule 1000g as so obtained lithium-containing transition metal oxide, added to by this granule in the pure water of 3.0L and stir, preparation is dispersed with the suspension of lithium-containing transition metal oxide.Then, add in this suspension and the pure water of 200mL is dissolved with Erbium trinitrate pentahydrate [Er (NO3)3·5H2O] aqueous solution of 5.42g.Above-mentioned suspension adds in the process of Erbium trinitrate pentahydrate aqueous solution, in order to the pH regulator of the solution by being dispersed with lithium-containing transition metal oxide is 9 and keeps constant, be suitably added the aqueous solution of nitric acid of 10 mass % or the sodium hydrate aqueous solution of 10 mass %.
Then, the interpolation of above-mentioned Erbium trinitrate pentahydrate solution carries out sucking filtration, washes further after terminating, and is then dried at 120 DEG C by gained powder, obtains the part on above-mentioned lithium-containing transition metal oxide surface and be attached with the powder of erbium hydroxide.Afterwards, by gained powder in air atmosphere, carry out the heat treatment of 5 hours in 300 DEG C, thus making positive active material granule.When so carrying out heat treatment at 300 DEG C, be attached to surface erbium hydroxide wholly or largely become hydroxyl oxidize erbium, therefore, become the state having hydroxyl oxidize erbium in the surface attachment of lithium-containing transition metal oxide granule.But, some situation about remaining with the state of erbium hydroxide, therefore, also there is the surface attachment at lithium-containing transition metal oxide granule to have the situation of erbium hydroxide.
For gained positive active material granule, utilizing scanning electron microscope (SEM) to observe, results verification is at the whole erbium compound uniformly disperseed and be attached with below mean diameter 100nm of lithium-containing transition metal oxide granule.It addition, measured the adhesion amount of erbium compound by ICP, result is counted relative to lithium-containing transition metal oxide granule (lithium nickel manganese cobalt composite oxide) as 0.20 mass % with er element conversion.
[making of anode plate]
Weigh above-mentioned positive active material granule, lithium metaborate, the white carbon black as conductive agent and the METHYLPYRROLIDONE solution being dissolved with polyvinylidene fluoride as binding agent in the mode that the mass ratio of positive active material granule and lithium metaborate with conductive agent with binding agent is 94.5:2.5:2.5, they mixing are prepared anode mixture slurry.It should be noted that, time mixing, only positive active material granule and lithium metaborate T.K.HIVISMIX (PRIMIXCorporation manufacture) are mixed in advance, form lithium metaborate to contact with positive active material granule and fully dispersed state, then add conductive agent and binding agent T.K.HIVISMIX (PRIMIXCorporation manufacture) mixes.
Then, above-mentioned anode mixture slurry is coated the two sides of the positive electrode collector formed by aluminium foil so that it is dry, then pass through stack and roll, and then the collector plate of installation aluminum, thus the two sides being produced on positive electrode collector is formed with the anode plate of positive electrode material mixture layer.
For gained anode plate, utilizing scanning electron microscope (SEM) to observe, the granule of the lithium metaborate of results verification below mean diameter 500nm is attached to the surface of lithium-containing transition metal oxide or the surface of erbium compound.Wherein, in operation conductive agent and binding agent mixed, lithium metaborate is from the situation of the sur-face peeling of positive active material granule for some, therefore, also has lithium metaborate to be not attached to positive active material granule and the situation that is contained in positive pole.It is attached to erbium compound is also present near erbium compound it addition, confirm lithium metaborate.
(making of negative pole)
Delanium as negative electrode active material, the CMC as dispersant (sodium carboxymethyl cellulose) and the SBR (butadiene-styrene rubber) as binding agent are mixed in aqueous with the mass ratio of 98:1:1, prepares cathode agent slurry.Then, this cathode agent slurry is coated equably the two sides of the negative electrode collector formed by Copper Foil, then make it dry, rolled by stack, and then the collector plate of nickel is installed.Thus, the two sides being produced on negative electrode collector is formed with the negative plates of anode mixture layer.It should be noted that the packed density of the negative electrode active material in this negative pole is 1.70g/cm3。
(preparation of nonaqueous electrolytic solution)
For the mixed solvent that ethylene carbonate (EC), Ethyl methyl carbonate (MEC) and dimethyl carbonate (DEC) mix with the volume ratio of 3:6:1, dissolve lithium lithium phosphate (LiPF6) it is the concentration of 1.0 mol/L.And then, prepare the nonaqueous electrolytic solution being dissolved with the vinylene carbonate (VC) of 2.0 mass % relative to above-mentioned mixed solvent and obtain.
(making of battery)
For so obtained positive pole and negative pole, configure separator at this two interpolar and be wound as helical form, then take out core, make spiral helicine electrode body.Then, the extruding of this spiral helicine electrode body is obtained the electrode body of platypelloid type.Afterwards, the electrode body of this platypelloid type and above-mentioned nonaqueous electrolytic solution are inserted in the shell body of aluminium laminate, make rechargeable nonaqueous electrolytic battery.It should be noted that this rechargeable nonaqueous electrolytic battery is of a size of thickness 3.6mm × width 35mm × length 62mm.It addition, this rechargeable nonaqueous electrolytic battery is charged to 4.40V, discharge capacity when being discharged to 2.75V is 800mAh.Hereinafter the battery so made is called battery A1.
The making of battery of the anode plate after air [use be exposed to]
When making anode plate, rolled by stack, be then exposed to air under the following conditions, in addition, make the battery (battery B1) using the anode plate after being exposed to air in the same manner as above-mentioned battery A1.
It is exposed to atmospheric condition
Temperature 30 DEG C, humidity 50% constant temperature and humidity cabinet in stand 5 days
(experimental example 2)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.55Mn0.20Co0.25]O2Shown lithium nickel manganese cobalt composite oxide, and when making anode plate, do not mix lithium metaborate, in addition, make battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A2.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B2) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A2.
(experimental example 3)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.55Mn0.20Co0.25]O2Shown lithium nickel manganese cobalt composite oxide, in addition, makes battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A3.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B3) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A3.
(experimental example 4)
When making anode plate, do not mix lithium metaborate, in addition, make battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A4.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B4) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A4.
(experimental example 5)
As positive active material granule, use Li1.06[Ni0.50Mn0.30Co0.20]O2Shown lithium nickel manganese cobalt composite oxide, in addition, makes battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A5.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B5) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A5.
(experimental example 6)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.50Mn0.30Co0.20]O2Shown lithium nickel manganese cobalt composite oxide, and when making anode plate, do not mix lithium metaborate, in addition, make battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A6.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B6) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A6.
(experimental example 7)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.50Mn0.30Co0.20]O2Shown lithium nickel manganese cobalt composite oxide, in addition, makes battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A7.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B7) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A7.
(experimental example 8)
Do not mix lithium metaborate when making anode plate, in addition, make battery in the same manner as above-mentioned battery A5.Hereinafter the battery so made is called battery A8.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B8) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A8.
(experimental example 9)
As positive active material granule, use Li1.06[Ni0.51Mn0.26Co0.23]O2Shown lithium nickel manganese cobalt composite oxide, in addition, makes battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A9.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B9) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A9.
(experimental example 10)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.51Mn0.26Co0.23]O2Shown lithium nickel manganese cobalt composite oxide, and when making anode plate, do not mix lithium metaborate, in addition, make battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A10.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B10) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A10.
(experimental example 11)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.51Mn0.26Co0.23]O2Shown lithium nickel manganese cobalt composite oxide, in addition, makes battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A11.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B11) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A11.
(experimental example 12)
Do not mix lithium metaborate when making anode plate, in addition, make battery in the same manner as above-mentioned battery A9.Hereinafter the battery so made is called battery A12.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B12) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A12.
(experimental example 13)
As positive active material granule, use Li1.06[Ni0.70Mn0.10Co0.20]O2Shown lithium nickel manganese cobalt composite oxide, in addition, makes battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A13.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B13) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A13.
(experimental example 14)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.70Mn0.10Co0.20]O2Shown lithium nickel manganese cobalt composite oxide, and when making anode plate, do not mix lithium metaborate, in addition, make battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A14.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B14) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A14.
(experimental example 15)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.70Mn0.10Co0.20]O2Shown lithium nickel manganese cobalt composite oxide, in addition, makes battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A15.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B15) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A15.
(experimental example 16)
Do not mix lithium metaborate when making anode plate, in addition, make battery in the same manner as above-mentioned battery A13.Hereinafter the battery so made is called battery A16.
It addition, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, the battery (battery B16) using the anode plate after being exposed to air is made in the same manner as above-mentioned battery A16.
The mensuration > of < initial charge/discharge efficiency
Use: be used without being exposed to the anode plate of air under these conditions and battery B1～battery B16 of utilizing the anode plate after being exposed to air under the conditions described above in battery A1～A16 of making and battery A1～A16 and making, carry out following discharge and recharge test, measure the initial charge/discharge efficiency of each battery.
The charge condition of the 1st circulation
Under the temperature conditions of 25 DEG C, constant-current charge is carried out until cell voltage becomes 4.4V (anodic potentials is calculated as 4.5V with lithio standard) with the constant current of 800mA, after cell voltage reaches 4.4V, carry out constant-potential charge with the constant voltage of 4.4V until electric current becomes 40mA.
The discharging condition of the 1st circulation
Under the temperature conditions of 25 DEG C, carry out constant-current discharge with the constant current of 800mA until cell voltage becomes 3.0V.
Stop
Resting interval between above-mentioned charging and discharging is set to 10 minutes.
Discharge and recharge under above-mentioned condition is set to 1 circulation, charging capacity measured value and discharge capacity measured value obtains the initial charge/discharge efficiency of the 1st circulation based on the formula (1) shown in following.
Initial charge/discharge efficiency (%)=discharge capacity/charging capacity × 100 (1)
< calculates > based on the deterioration in characteristics index exposed
In the above-mentioned initial charge/discharge efficiency obtained, initial charge/discharge efficiency without exposure to air (when use is not exposed to the anode plate of air) is set to " unexposed initial efficiency ", by have be exposed to air (use be exposed to air after anode plate time) initial charge/discharge efficiency be set to " having the initial efficiency of exposure ", based on following shown formula (2), the difference of the unexposed initial efficiency of corresponding battery and the initial efficiency having exposure calculate based on the deterioration in characteristics index exposed.
Based on deterioration in characteristics index=(unexposed initial efficiency)-(having the initial efficiency of exposure) (2) exposed
Its result is concluded and is shown in table 1 below.
[table 1]
Result from above-mentioned table 1, particle surface at lithium-containing transition metal oxide is attached with the battery of hydroxyl oxidize erbium and lithium metaborate and nickel and the experimental example 1,9,13 that the difference of the molar ratio of manganese is more than 0.25 compared with the battery of experimental example 2～4,5～8,10～12,14～16, is greatly reduced based on the deterioration in characteristics index exposed.In addition, only it is attached with the battery of experimental example 3,7,11,15 of lithium metaborate with the battery of the experimental example 4,8,12,16 being only attached with hydroxyl oxidize erbium compared with the battery of the experimental example 2,6,10,14 all not possessing these, deterioration in characteristics index based on atmospheric exposure has no change substantially, but the battery having both the experimental example 1,9,13 of both batteries composition of experimental example 3,7,11,15 and experimental example 4,8,12,16 is greatly improved the improvement of above-mentioned each effect as seen.Obtain the reason of such result it is believed that as described below.
It is believed that, when the surface of lithium-containing transition metal oxide is attached with the battery of experimental example 1 of hydroxyl oxidize erbium and lithium metaborate simultaneously, can suppress by being exposed to the reason of the deterioration in characteristics that air causes and LiOH reaction of formation (specifically by hydroxyl oxidize erbium, it is present in moisture and the lithium-containing transition metal oxide reaction on the surface of lithium-containing transition metal oxide, cause the displacement reaction of Li and the hydrogen being positioned at lithium-containing transition metal oxide surface layer, thus capture Li from lithium-containing transition metal oxide and generate the reaction of LiOH) carrying out, therefore, when carrying out discharge and recharge after can reducing the exposure to air, efficiency for charge-discharge reduces such by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes.
Additionally, the surface of lithium-containing transition metal oxide can reduce due to the interaction of lithium metaborate and hydroxyl oxidize erbium, therefore, the moisture in air is suppressed to the absorption of lithium-containing transition metal compound.It is believed that, owing to this water adsorption amount can be reduced, therefore it is suppressed further by the carrying out of the reason and above-mentioned LiOH reaction of formation that are exposed to the deterioration in characteristics that air causes, it is possible to reduce by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes further.By playing such synergy, can suppress by being exposed to the reason of the deterioration in characteristics that air causes and above-mentioned LiOH reaction of formation, it is as a result, it is possible to rapidly reduce and reduced such by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes by efficiency for charge-discharge when carrying out discharge and recharge after being exposed to air.
It should be noted that it is believed that the effect played by boron compound when the interaction of above-mentioned boron compound and hydroxyl oxidize erbium coexists for boron compound and rare earth compound, do not play when boron compound individualism.
When being only attached with the battery of experimental example 4,8,12,16 of hydroxyl oxidize erbium, it is impossible to obtain above-mentioned synergy produced by hydroxyl oxidize erbium and lithium metaborate.Namely, although owing to the existence of hydroxyl oxidize erbium can somewhat suppress to be exposed to the worsening reason of air and above-mentioned LiOH reaction of formation, but owing to being absent from boron compound, therefore cannot reducing the surface energy of lithium-containing transition metal oxide, moisture is many to the absorption quantitative change on lithium-containing transition metal oxide surface.Accordingly, it is believed that accelerate to be exposed to the worsening reason of air and the carrying out of above-mentioned LiOH reaction of formation, it is impossible to fully suppress by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes.
When being only attached with the battery of experimental example 3,7,11,15 of lithium metaborate, also cannot obtain above-mentioned synergy produced by hydroxyl oxidize erbium and lithium metaborate.That is, as described above, it is believed that the surface that lithium metaborate individualism and will not causing when not coexisting with rare earth compound is caused by lithium metaborate can reduction.Accordingly, it is believed that the absorption to lithium-containing transition metal oxide of the moisture in air cannot be suppressed, accelerate the carrying out of above-mentioned LiOH reaction of formation.Accordingly, it may be concluded that in the battery of experimental example 3,7,11,15, owing to being absent from rare earth compound, therefore, the inhibition of above-mentioned LiOH reaction of formation produced by rare earth compound also cannot be obtained.Namely, it can be seen that experimental example 2,6,10,14 and experimental example 3,7,11,15 become substantially equal result, as experimental example 3,7,11,15, when only making boron compound adhere to, it is impossible to be inhibited the effect by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes.
When the battery of experimental example 2,6,10,14, both hydroxyl oxidize erbium and lithium metaborate are not attached to the surface of lithium-containing transition metal compound, it can be considered that, cannot obtain produced by hydroxyl oxidize erbium effect and produced by hydroxyl oxidize erbium and lithium metaborate synergy, thus the reaction of above-mentioned generation LiOH cannot be suppressed, it is impossible to suppress by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes.
It addition, in the battery of experimental example 5, both hydroxyl oxidize erbium and lithium metaborate are attached to the surface of lithium-containing transition metal compound.But, the difference of the molar ratio of nickel and manganese is 0.20, therefore, with nickel compared with the experimental example 1,9,13 that the difference of the molar ratio of manganese is more than 0.25, it is impossible to fully suppress by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes.It is believed that this be due to, when the difference of the molar ratio of nickel and manganese is less than 0.20, as experimental example 6, originally under the state not having surface-element also little by the deterioration being exposed to the initial stage charge-discharge characteristic that air causes, unconfirmed improve effect to produced by hydroxyl oxidize erbium and lithium metaborate.
(the 2nd experimental example)
(experimental example 17)
When making positive active material granule, as rare earth compound, use samaric nitrate hexahydrate to replace Erbium trinitrate pentahydrate, in addition, make battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A17.
What gained positive active material was attached to the Samarium trihydroxide. on surface wholly or largely becomes hydroxyl oxidize samarium by heat treatment, is attached to the state on the surface of positive active material granule for hydroxyl oxidize samarium.Wherein, some situation about remaining with the state of Samarium trihydroxide., therefore, also there is Samarium trihydroxide. to be attached to the situation on surface of lithium-containing transition metal oxide granule.For this positive active material granule, utilizing scanning electron microscope (SEM) to observe, results verification is at the whole samarium compound uniformly disperseed and be attached with below mean diameter 100nm of lithium-containing transition metal oxide granule.It addition, measured the adhesion amount of samarium compound by ICP, result is counted relative to lithium nickel manganese cobalt composite oxide as 0.20 mass % with the conversion of samarium element.
Additionally, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, similarly make with above-mentioned battery A17 and use the corresponding battery (battery B17) being exposed to the anode plate after air with battery A17.
(experimental example 18)
When making anode plate, do not mix lithium metaborate, in addition, make battery in the same manner as above-mentioned battery A17.Hereinafter the battery so made is called battery A18.
Additionally, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, similarly make with above-mentioned battery A18 and use the corresponding battery (battery B18) being exposed to the anode plate after air with battery A18.
(experimental example 19)
When making positive active material granule, as rare earth compound, use neodymium nitrate hexahydrate to replace Erbium trinitrate pentahydrate, in addition, make battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A19.
What gained positive active material granule was attached to the Neodymium hydroxide on surface wholly or largely becomes hydroxyl oxidize neodymium by heat treatment, is attached to the state on the surface of lithium-containing transition metal oxide for hydroxyl oxidize neodymium.Wherein, some situation about remaining with the state of Neodymium hydroxide, therefore, also there is Neodymium hydroxide to be attached to the situation on surface of lithium-containing transition metal oxide granule.For this positive active material, utilizing scanning electron microscope (SEM) to observe, the neodymium compound of results verification below mean diameter 100nm is uniformly dispersed and is attached to the whole surface of lithium-containing transition metal oxide granule.It addition, measured the adhesion amount of neodymium compound by ICP, result converts in neodymium element, is 0.20 mass % relative to lithium nickel manganese cobalt composite oxide.
Additionally, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, similarly make with above-mentioned battery A19 and use the corresponding battery (battery B19) being exposed to the anode plate after air with battery A19.
(experimental example 20)
When making anode plate, do not mix lithium metaborate, in addition, make battery in the same manner as above-mentioned battery A19.Hereinafter the battery so made is called battery A20.
Additionally, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, similarly make with above-mentioned battery A20 and use the corresponding battery (battery B20) being exposed to the anode plate after air with battery A20.
Use the battery utilizing the battery A17～battery A20 not being exposed to the anode plate of air under these conditions and make and the battery B17～battery B20 utilizing the anode plate after being exposed to air in battery A17～battery A20 under these conditions to make, calculate the deterioration in characteristics index based on exposure in the same manner as above-mentioned 1st experimental example.The result of its result Yu the battery of experimental example 1,4 is concluded in the lump and is shown in table 2 below.
[table 2]
Result such as above-mentioned table 2 is known, it is used in that the part on surface is attached with samarium compound, neodymium compound replaces the battery of experimental example 17,19 of lithium-containing transition metal oxide of erbium compound compared with the battery of the experimental example 18,20 being added without boron compound of the battery corresponding respectively to experimental example 17,19, is greatly reduced based on the deterioration in characteristics index exposed.
As can be known from the above results, even if being samarium compound, neodymium compound, it is also possible to obtain the effect same with the situation of erbium compound.Thus it is believed that, when making the surface that rare earth compound is attached to lithium-containing transition metal oxide, it is suppressed by the reaction of the reason and above-mentioned generation LiOH that are exposed to the deterioration in characteristics that air causes, thus can reduce by being exposed to the initial stage charge-discharge characteristic deterioration that air causes, it is believed that this action effect is the effect common with rare earth compound.
It should be noted that when the result of the battery of experimental example 1,17,19 is compared, it is thus identified that, the battery of experimental example 1 and experimental example 17, experimental example 19 battery compared with reduce by exposing the deterioration in characteristics index caused.It follows that in rare earth element, it is particularly preferred to for erbium compound.
(the 3rd experimental example)
(experimental example 21)
When making anode plate, as boron compound, use lithium tetraborate to replace lithium metaborate, in addition, make battery in the same manner as above-mentioned battery A1.Hereinafter the battery so made is called battery A21.
Additionally, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, similarly make with above-mentioned battery A21 and use the corresponding battery (battery B21) being exposed to the anode plate after air with battery A21.
(experimental example 22)
As positive active material granule, use the Li of unattached erbium compound1.06[Ni0.55Mn0.20Co0.25]O2Shown lithium nickel manganese cobalt composite oxide, in addition, makes battery in the same manner as above-mentioned battery A21.Hereinafter the battery so made is called battery A22.
Additionally, when making anode plate, rolled by stack, be then exposed to air under these conditions, in addition, similarly make with above-mentioned battery A22 and use the corresponding battery (battery B22) being exposed to the anode plate after air with battery A22.
Use: the battery B21～battery B22 utilizing the anode plate after being exposed to air under these conditions to make in the battery of the battery A21～battery A22 utilizing the anode plate not being exposed to air under these conditions to make and battery A21～battery A22, calculate in the same manner as above-mentioned 1st experimental example based on the deterioration in characteristics index exposed.The result of its result Yu the battery of experimental example 1,3 is concluded in the lump and is shown in Table 3 below.
[table 3]
Result from above-mentioned table 3, the part using surface is attached with compared with the battery of the experimental example 22 of the unattached erbium compound that lithium tetraborate replaces the battery of experimental example 21 of lithium-containing transition metal oxide of lithium metaborate corresponding with the battery with experimental example 21, is greatly reduced based on the deterioration in characteristics index exposed.
Even if by result above it can be seen that the effect same with lithium metaborate can also be obtained for lithium tetraborate, it is believed that this result is to use the common effect obtained when the compound comprising boron.It should be noted that when the result of the battery of experimental example 1,21 is compared, it is thus identified that the battery of experimental example 1, compared with the battery of experimental example 21, reduces based on the deterioration in characteristics index exposed.It follows that in boron compound, it is particularly preferred to lithium metaborate.
Industrial applicability
The positive electrode for nonaqueous electrolyte secondary battery of one scheme of the present invention and the rechargeable nonaqueous electrolytic battery using it can apply to the driving power supply of the personal digital assistant devices such as such as mobile phone, notebook computer, smart mobile phone, panel computer terminal, the purposes in particular for high-energy-density.And then, it is also possible to expect carrying out in electric automobile (EV), mixed power electric car (HEV, PHEV), the such high output purposes of electric tool.
Description of reference numerals
1 positive pole
2 negative poles
3 separators
4 positive pole collector plates
5 negative pole collector plates
6 aluminium lamination pressure shell bodies
7 heat-sealing portions
11 rechargeable nonaqueous electrolytic batteries

Claims (12)

1. a positive electrode for nonaqueous electrolyte secondary battery, it possesses: positive active material granule and boron compound,
Described positive active material granule comprises lithium-containing transition metal oxide,
Described lithium-containing transition metal oxide has rare earth compound in its surface attachment, and
Described lithium-containing transition metal oxide contains nickel and manganese, and the molar ratio of described nickel is more than the molar ratio of described manganese, and the difference of the molar ratio of described nickel and described manganese is more than 0.25.
2. positive electrode for nonaqueous electrolyte secondary battery according to claim 1, wherein, the difference of the molar ratio of described nickel and described manganese is less than 0.60.
3. positive electrode for nonaqueous electrolyte secondary battery according to claim 1 and 2, wherein, the molar ratio of the nickel of described lithium-containing transition metal oxide is more than 0.5.
4. the positive electrode for nonaqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein, described boron compound is attached to the surface of described lithium-containing transition metal oxide.
5. the positive electrode for nonaqueous electrolyte secondary battery according to any one of Claims 1 to 4, wherein, described boron compound is at least one in boric acid, Lithium biborate, lithium metaborate, lithium tetraborate.
6. the positive electrode for nonaqueous electrolyte secondary battery according to any one of Claims 1 to 5, wherein, the particle diameter of described boron compound less than described lithium-containing transition metal oxide particle diameter 1/10.
7. the positive electrode for nonaqueous electrolyte secondary battery according to any one of claim 1～6, wherein, described rare earth compound is at least one in hydroxide, oxyhydroxide, oxide, carbonate compound, phosphate cpd and fluorine compounds.
8. positive electrode for nonaqueous electrolyte secondary battery according to claim 7, wherein, described rare earth compound is at least one in hydroxide and oxyhydroxide.
9. the positive electrode for nonaqueous electrolyte secondary battery according to any one of claim 1～8, wherein, rare earth element contained in described rare earth compound is at least one in erbium, samarium, neodymium.
10. the positive electrode for nonaqueous electrolyte secondary battery according to any one of claim 1～9, wherein, described boron compound is calculated as more than 0.005 mass % and below 5 mass % relative to the ratio of the gross mass of described lithium-containing transition metal oxide with boron element conversion.
11. the positive electrode for nonaqueous electrolyte secondary battery according to any one of claim 1～10, wherein, described lithium-containing transition metal oxide is the form of the second particle that primary particle is combined into.
12. positive electrode for nonaqueous electrolyte secondary battery according to claim 11, wherein, the particle diameter of the primary particle of described lithium-containing transition metal oxide is more than 100nm and less than 10 μm, and the particle diameter of the second particle of described lithium-containing transition metal oxide is more than 2 μm and less than 30 μm.
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